Polymerization of olefins



?atentecl Sept. 9, 1941 Henry J. Welge, Bryan, Tex.

No Drawing. Application August 30, 1938, Serial N0. 227,597

3 Claims.

This invention relates to the polymerization of mono-olefin hydrocarbons to produce higher homologues or polymers thereof. An especially important application of the invention is in the polymerization of olefins of relatively low boiling'point, such as propylene, but'ylene or other mono olefins which aregases at ordinary temperatures, to form polymerized hydrocarbonsparticularly dimers of the original hydrocarbonof higher boiling point, which are liquids at ordinary temperatures and whose boiling points lie within the boiling point range of motor fuels.

Thisapplication isa continuation-in-part ofmy application Serial No. 136,174, filed April 10,.

Polymerization of mono-olefins at moderate temperatures requires the use of some catalyst, and the present invention is concerned primarily with the use of an advantageous type of catalyst for this purpose.

It is well known that lower hydrocarbons belonging to the olefinic series react chemically with, and dissolve in, strong, concentrated acids such as sulphuric or phosphoric acids, to give an addition product of the acid and the hydrocarbon. When this addition. product is heated to a suitable temperature which depends-on the hydrocarbon used, .a polymerization of two or more molecules of the hydrocarbon occurs.

Furthermore, an alternative way in which the desired polymerization may be effected'consists in first heating separately the acid and the hydrocarbon, and then bringing them into contact with each other. 1

When either of these processes are used to achieve the polymerization of olefinic hydrocarbons, containers and equipment must be employed which will withstand the corrosive action of. fairly concentrated acids. The operation of the processes also has other disadvantages inherent in the handling of corrosive and dangerous liquids.

Furthermore, liquid hydrocarbons formed by the reaction tend to dissolve in or emulsify with,

the liquid acid, causing difliculty in the complete separation and recovery of the hydrocarbon such normally gaseous out hereinafter or will be apparent from the following description.

These objects are attained, in accordance with this invention, by the use of a catalytic-agent which has astrongly acid reaction but which is solid at temperatures sufi'icient to cause the desired polymerization to take place.

If a polybasic acid be partially neutralized by, say, a strong base, an acid salt may be produced which is, in general, a solid, sometimes even at somewhat elevated temperatures, yet still has a more or less strongly acid reaction, depending on which polybasic acid be originally chosen.

Now, among the polybasic acids which are of lowenough cost to be considered for making catalysts. for industrial polymerization processes, sulphuric acid is unusual in the respect that its acid salts have a strongly acid reaction. Consequently, the type of catalyst. which I propose to use for polymerization comprises, in general, solid salts of sulphuric acid having a strongly acid reaction. As temperatures somewhat above atmospheric temperature are ordinarily desirable in order to cause the polymerization reaction to proceed at 'a sufliciently fast rate for commercial utilization of the process, I prefer to employ as catalysts salts of the above type which are solid at such temperatures.

Preferred examples of such catalysts are bisulphates of sodium, potassium and ammonium, which may be referred .to generally as bisulphates of alkali metals. Other examples are other acid sulphates of alkali metals such as Na3H(SO4)2 and acid sulphates of other metals,

' such as A12(SO4) 3.H2S04.3H20 and FeSOhmSCh.

The catalyst may be used in the form of lumps 'or particles of convenient size, consisting substantially wholly of thecatalyst salt, and I prefer to use compounds which may be obtained in type above soluble in products or in the separation -of the acid for reuse.

The principal object of the present invention is to ,provide a method of polymerizing monoole fin's, and particularly normally gaseous'monoolefins, which is free from the above-mentioned dimculties, and in catalysts of low cost may beemployed.

Other objects of the which readily available the form of crystals of suflicie t size to permit free passage of the hydrocar on fluid to be. treated through a body of the catalyst.

A further advantage of the catalysts of the described is that they are completely thereof become coated or contaminated by accumulationot gummy or carbonaceous imp'url-. ties thereon, during use, tosuch an extent as to impair the catalytic action thereof, the catalyst material, which is ordinarily employed in the form of a pervious bed, layer, or column, may be washed with hot water or moist steam to dissolve and carry awaythe surface portions thereof together with the accumulated impurities, which invention will be pointed enables the activity of the catalyst to be easily water, so that in case the surfaces cific catalyst employed, the particular pheric temperature,

with or deposited upon relatively inert carrier of the catalyst by materials, such as clay or pumice, as by crystallization or precipitation of the catalytic agent upon such carrier materials,.or by impregnating the carrier with the melted catalyst.

In carrying out the invention, a mono-olefin, in gaseous state (either gas or vapor), is brought into contact with a solid. catalyst of the type above described, at a temperature above atmospheric temperature and below the melting point of the catalyst, and is subjected to such contact for a suificient length of time to cause polymerization. In commercial operation, the temperature should in most cases beabout 100 C. or above, in order to provide a sufliciently rapid rate of reaction. "The upper limit of temperature is, of course, fixed by the melting point of the solid catalyst, and may in some cases be infiuenced also by a desire to avoid the of higher polymers or other complex products whose formation is promoted by high temperatures. The temperature is subject, however, to considerable variation, depending upon the speolefln or olefins treated, and the rate and completeness of reaction desired.

It will be understood that the pressure under which the polymerization reaction is carried out is such as to maintain the olefin undergoing treatment in the gaseous state at the reaction temperature employed.

The reaction will, in general, proceed at a the reacting 'olefins are subjected. Consequently, the reaction preferably is conducted at a pressure above normal atmospheric pressure.

The polymer or polymers produced may be allowed to condense in the reaction chamber and may be removed therefrom in liquid form, either continually or at intervals, or may be conducted away in vapor form and condensed or otherwise collected. It will be understood that the process may be applied either to a pure mono-olefin or to a mixture of mono-olefins (in which case one or more of the olefins may be caused to polymerize) or to a mixture of one or more mono-olefins with one or more other hydrocarbons or other fluids, such as by-product'gases from petroleum cracking operations.

In general, I have found that water vapor in at least limited proportion must, be present before polymerization will be catalyzed by acid sulphates such as described above. I have further discovered that chiefly those acid sulphates which are hygroscopic or which have an aflinity for water are effective as catalysts for polymerization of olefins, and particularly those acid sulphates which retain their affinity for water at temperatures somewhat above normal atmos such as, for example, sodium bisulphate, NaI-IS O4, which readily takes up water to formv NaHSO4.HzO. In some cases, the admixture with acid sulphates, in the melted state, if desired, of other hygroscopic substances such as aluminum sulphate which, in themselves, may or may not have an acid reaction, may increase the effectiveness of the resulting catalyst material.

The invention thus contemplates carrying out formation the polymerization ofmono-olefins byzcontact with the solid catalyst in the presence of a limited proportion of water vapor, either for the purpose of promoting the polymerizing reaction or for preventing deterioration or decomposition loss of water. Such water vapor maybe derived from water either physically or chemically associated with the solid catalyst, or may be introduced, preferably as steam, along with the olefin. In any'cases where the presence of water tends to cause other reactions than the desired polymerization, such as hydrolysis (which tends to occur particularly with lower members of the oleflnic series such as butylene), the proportion of water present should be so limited as to substantially minimize the occurrence of such other reactions, and should be relatively small as compared with the molecular proportion of olefin present. Furthermore, at anyparticular temperature of operation, the proportion of water present (either added as steam or deexception of a thin more rapid rate, the higher the pressure to which 40 suflicien rived from the catalyst material) should be kept sufficiently low to substantially avoid the pres.- ence of free water in liquid state and thus avoid formation of any considerablequantity of aqueous solution of the catalyst salt, with the possible film of aqueous solution on the surface of the particles of catalyst. It will be understood, therefore, that references herein to the presence of water vapor are intended to refer to water vapor which is either introduced in .vapor form or derived from water associated with the solid catalyst, and that the molecular proportion of water present in vapor form should usually not be more than a small fraction of the molecular proportion of olefins which is caused to react.

Occasionally, in practicing my invention, it happens that the quantity of water present is v t to cause formation of a thin film of liquid on the surfaces of the catalyst, which may be due either to condensation of water and for-,

mation of an aqueous solution of the catalyst or to formation of a hydrated form ,of the catalyst which melts at the temperature employed, even though such temperature is below the melting point of the catalyst material originally employed. The liquid film thus formed mayin some cases flowdown to a lower point, in the apparatus. While it will be understood that the conditions are preferably so chosen that such an occurrence is substantially avoided, it maybe difflcult to eliminate it completely when employing catalyst materials of a hygroscopic nature. Accordingly, it is to be understood that references herein and in the appended claims to use of a solid catalyst or to operation at temperatures below the melting point of the catalyst are notintended to exclude operation under-conditions in which such, liquid films are formed. In

any event, the major portion of the catalyst ma-.- terial with which'the olefin is treated. will exist higher temperatures, in order to cause polymerization of one after another of such olefins, and

gaseous mixture contain-- heated in any the polymerized'products formed in each of these stages are preferably separately collected, as by condensation, prior to the next succeeding stage.

-Treatment in successive stages, with condensa- ,consist largely of d'i-isobutylene.

product thus obtained is useful as a superior According to a preferred procedure, the catalyst may be packed in a tower or chamber, either with or without other packing material, and the pervious body of catalyst thus provided may be suitable manner, as by providing a steam jacket around the tower or chamber, and the olefin or olefins, either alone or together with other hydrocarbons. may be passed therethrough in gaseous state. An alternative arrangement consists in passing the olefin-containing gas or vapor over layers of the catalyst supported on shelves or plates in a heated chamber, or over layers of catalyst within heated horizontal tubes. It may be further desirable, in some cases, to heat the gas or vapor which is to be subjected to the polymerization process, in addition to, or instead of, heating the catalyst chamber. heat to maintain the reaction chamber at the desired temperature, it should be borne in mind that the above-described polymerization reactions are exothermic, and that the heat of reaction will furnish part of the necessary heat.

As another alternative method, the olefin or olefin-containing gaseous fluid may first be mixed or subjected to contact with the solid catalyst, for any desired period of time, at a relatively low temperature, for example, at or near atmospheric temperature, to cause formation of an addition product of thecatalyst salt and the olefin or olefins, and the resulting mixture, or the addition product so formed after separation from unreacted olefin or other hydrocarbon materials present, may then be heated to a higher temperature, such as about 100 C. or above but below the melting po' t of the catalyst salt, to convert the addition product into the desired polymerized product, with regeneration of the catalyst salt in solid condition. The polymer-or polymers so formed may be separated in liquid In supplying form, or may be withdrawn in vapor form and then condensed.

As a specific example of the present invention, one may employ a catalyst consisting substantially of sodium bisulphate in divided condition, but containing also a small percentage of water, say about 8 more or less, by weight of the catalyst. Gaseous lsobutylene and this catalyst may be brought into contact at a pressure above normal atmospheric pressure, say at a pressure between 5 and atmospheres, and at a temperature above atmospheric temperature and below the melting point of the catalyst, and preferably between about 100 C. andthe melting point of the catalyst, for example, about C. to C. Since the critical temperature of isobutylene is in the neighborhood of 127 C. it will necessarily be present in the gaseous state at the start of the reaction when temperatures higher than this are used. At temperatures below the critical temperature, the pressure should be such as to maintain the lsobutylene in the gaseous state, as noted above. Thisprocedure causes the formation of polymerized products of lsobutylene which are liquids at ordinary temperatures, and which motor fuel of high anti-knock properties.

Inasmuch as sodium bisulphate, NaHSO4, is hygroscopic, it will frequently be found that the act of grinding, or otherwise dividing, and classifying or handling this substance in the openair, preparatory to use thereof as a catalyst in the practice of my invention as described above, will cause the absorption of enough water to enable the polymerization to take place, without the necessity of adding additional water to the solid catalyst.

As a second specific example of my invention, one may proceed as in the preceding example, but employ a catalyst consisting substantially of potassium bisulphate in divided condition, together with a small percentage of water, say about 3%, more or less, by weight of the catalyst. Since the melting point of potassium bisulphate is higher than that of sodium bisulphate, somewhat higher temperatures may be used in this case, if desired.

I claim: 1. The method of polymerizing mono-olefins which comprises subjecting a mono-olefin in gaseous state to contact with a catalyst comprising a bisulphate of an alkali metal in solid form, at a temperature between about 100 C. and the melting point of said bisulphate, and in the presence of water vapor substantially avoid the presence of free water in liquid state at said temperature.

2. The method of polymerizing mono-oleflns which comprises subjecting a mono-olefin in gaseous state to contact with a bisulphate of an alkali metal in solid form, at a temperature between about 100 C. and 180 C., and in the presence of water vapor in sufllciently small proportion to substantially avoid the presence of free water in liquid state at said temperature. V

3. The method of polymerizing mono-oleflns which comprises subjecting a mono-olefin in gaseous state to contact with a catalyst comprising an acid sulphate of aluminum in solid form, temperature between about 100 C. and the melting point of said acid tion to substantially avoid the presence of free water in liquid state at said temperature.

may .nwra-c'dl The liquid in sumciently small proportion to ata.

sulphate, and in the Pres- .ence' of water vapor in sufflciently small propor- 

